致密气藏储层干化剂在超临界CO_2中的溶解性及增溶研究
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摘要
以离子型碳化物A_XC_Y作为干化主剂注入致密气藏储层中与地层水发生化学反应能够消耗地层水、降低储层含水饱和度,从而提高气体渗流能力。但由于致密气藏储层孔喉较小,固体A_XC_Y颗粒通常难以直接注入其中,因此需要寻找一种有效的干化剂注入方法。通过实验研究发现,超临界二氧化碳(SCCO_2)能够溶解少量无机化合物A_XC_Y,且降压后A_XC_Y析出。故可采用SCCO_2作为输送剂将A_XC_Y溶解并将其有效带入致密储层孔隙中。以此为基础,本文进一步研究了温度和压力对A_XC_Y在SCCO_2中的溶解度的影响;并对多种物质进行测试,优选出了最佳的夹带剂及其用量对A_XC_Y进行增溶。研究结果表明:A_XC_Y可溶解于SCCO_2,在8MPA、40℃下的溶解度为0. 0005mol·mol;且溶解度随压力的升高而增加,但温度对溶解度的影响随压力的变化呈现出非单一的变化规律;此外,以乙醇作为夹带剂具有明显且优于其他物质的增溶效果,其最佳摩尔浓度为10%。
The chemical reaction of A_XC_Ywith formation water can deplete the water,reduce the water saturation and improve the gas seepage capacity of tight gas reservoir.However,the pore and throat in tight reservoir is so small that the A_XC_Yparticles are difficult to be injected into them.Therefore,it is necessary to find an effective injection method for drying agent.Through the experiment,we discovered that SCCO_2 could dissolve a small amount of A_XC_Yand A_XC_Yseparated out when the pressure decreased.Therefore,SCCO_2 can be used as transport agent to dissolve A_XC_Yand bring it into tight gas reservoir.On the basis,this paper further studied the solubility of A_XC_Yin SCCO_2 under different temperature and pressure,and also selected the optimal cosolvent and its dosage to enhance solubility.The results show that the A_XC_Yis soluble in SCCO_2 and the solubility is 0. 0005mol·mol~(-1)under40℃ and 8MPa.When temperature is constant,the solubility increase with the increaseing of pressure,but the influence of temperature shows non-monotone change on solubility with the change of pressure.The solubilizing effect of cosolvent of ethanol was obvious and superior to other substances,and its optimal dosage was 10%.
The chemical reaction of A_XC_Ywith formation water can deplete the water,reduce the water saturation and improve the gas seepage capacity of tight gas reservoir.However,the pore and throat in tight reservoir is so small that the A_XC_Yparticles are difficult to be injected into them.Therefore,it is necessary to find an effective injection method for drying agent.Through the experiment,we discovered that SCCO_2 could dissolve a small amount of A_XC_Yand A_XC_Yseparated out when the pressure decreased.Therefore,SCCO_2 can be used as transport agent to dissolve A_XC_Yand bring it into tight gas reservoir.On the basis,this paper further studied the solubility of A_XC_Yin SCCO_2 under different temperature and pressure,and also selected the optimal cosolvent and its dosage to enhance solubility.The results show that the A_XC_Yis soluble in SCCO_2 and the solubility is 0. 0005mol·mol~(-1)under40℃ and 8MPa.When temperature is constant,the solubility increase with the increaseing of pressure,but the influence of temperature shows non-monotone change on solubility with the change of pressure.The solubilizing effect of cosolvent of ethanol was obvious and superior to other substances,and its optimal dosage was 10%.
引文
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[18]Koga Y,Iwai Y,Hata Y,et al.Influence of cosolvent on solubilities of fatty acids and higher alcohols in supercritical carbon dioxide[J].Fluid Phase Equilibria,1996,125(1):115-128.
[19]Su B,Lv X,Yang Y,et al.Solubilities of Dodecylpolyoxyethylene Polyoxypropylene Ether in Supercritical Carbon Dioxide[J]. Journal of Chemical&Engineering Data,2006,51(2):542-544.
[20]窦梓铭.溶质在含与不含夹带剂的超临界二氧化碳中溶解度研究[D].北京:北京化工大学,2012.
[21]李佳林.固体溶质与超临界二氧化碳多元体系相平衡的研究[D].北京:北京化工大学,2011.
[22]曹维良,刘鑫,张敬畅.聚合物-溶剂-超临界CO2三元体系的相行为[J].物理化学学报,2001,17(8):757-760.
[2]郑志红,李登华,王志欣,等.我国重点盆地致密油气资源潜力评价[J].中国矿业,2017,26(08):22-29.
[3]魏新善,胡爱平,赵会涛,等.致密砂岩气地质认识新进展[J].岩性油气藏,2017,29(01):11-20.
[4]Amiri M,Zahedi G,Yunan M H.Water saturation estimation in tight shaly gas sandstones by application of Progressive Quasi-Static(PQS)algorithm-A case study[J].Journal of Natural Gas Science&Engineering,2015,22:468–477.
[5]Masters J A.Deep basin gas trap,western canada[J].Aapg Bulletin,1979,63(2):152-181.
[6]赖南君,叶仲斌,刘向君,等.低渗透致密砂岩气藏水锁损害室内研究[J].天然气工业,2005(04):125-127.
[7]熊钰,莫军,李佩斯,等.致密储层干化主剂筛选评价与配方研制[J].西南石油大学学报(自然科学版),2018,40(01):165-172.
[8]邹才能,朱如凯,吴松涛,等.常规与非常规油气聚集类型、特征、机理及展望——以中国致密油和致密气为例[J].石油学报,2012,33(02):173-187.
[9]Nelson P H. Pore-throat sizes in sandstones,tight sandstones,and shales[J]. Aapg Bulletin,2009,93(3):329-340.
[10]王瑞和,倪红坚,宋维强,等.超临界二氧化碳钻井基础研究进展[J].石油钻探技术,2018,46(02):1-12.
[11]Mouahid A,Dufour C,Badens E.Supercritical CO2extraction from endemic corsican plants; comparison of oil composition and extraction yield with hydrodistillation method[J].Journal of CO2Utilization,2017,20:263-273.
[12]Melo M M R D,Silvestre A J D,Silva C M.Supercritical fluid extraction of vegetable matrices:Applications,trends and future perspectives of a convincing green technology[J]. Journal of Supercritical Fluids,2014,92(8):115-176.
[13]李金恒.超临界二氧化碳介质中溴化钯催化炔烃环三聚反应[J].化学学报,2004,62(3):341-343.
[14]吕鉴泉,刘忠文,刘惠娜,等.超临界CO2流体萃取金线莲中的腺苷[J].化学研究与应用,2017,29(04):560-564.
[15]岳红,赵晓莉,张颖.超临界二氧化碳萃取柿叶黄酮的工艺研究[J].化学研究与应用,2005(03):421-423.
[16]Fan J L,Hou Y C,Wu W Z,et al.Levulinic acid solubility in supercritical carbon dioxide with and without ethanol as cosolvent at different temperatures[J].J Chem Eng Data,2010,55:2316-2321.
[17]Jing Y,Hou Y C,Wu W Z,et al.Solubility of 5-hydroxymethylfurfural in supercritical carbon dioxide with and without ethanol as cosolvent at(314.1 to 343.2)K[J].J Chem Eng Data,2011,56:298-302.
[18]Koga Y,Iwai Y,Hata Y,et al.Influence of cosolvent on solubilities of fatty acids and higher alcohols in supercritical carbon dioxide[J].Fluid Phase Equilibria,1996,125(1):115-128.
[19]Su B,Lv X,Yang Y,et al.Solubilities of Dodecylpolyoxyethylene Polyoxypropylene Ether in Supercritical Carbon Dioxide[J]. Journal of Chemical&Engineering Data,2006,51(2):542-544.
[20]窦梓铭.溶质在含与不含夹带剂的超临界二氧化碳中溶解度研究[D].北京:北京化工大学,2012.
[21]李佳林.固体溶质与超临界二氧化碳多元体系相平衡的研究[D].北京:北京化工大学,2011.
[22]曹维良,刘鑫,张敬畅.聚合物-溶剂-超临界CO2三元体系的相行为[J].物理化学学报,2001,17(8):757-760.